Dyeing preparations and their conversion into dyestuffs



Patented May 22, 1934 UNITED f STATES PATENT OFFICE DYEING PREPARATIONS AND THEIR CON VERSION INTO DYESTUFFS H Arthur Zitscher and Wilhelm Seidenfaden, Oflenbach-on-the-Main, Germany, assignors to General Aniline Works, Inc., New York, corporation of Delaware N. Y., a

No Drawing. Application June 16, 1933, Serial 8 (Claims.

The present invention relates to dyeing preparations and to their conversion, into dyestufis.

These dyeing preparations contain an antidiazo-sulfonate corresponding to the probable general formula:

140,747), (6-halogenor 6-arylamino-2-hydroxynaphthalene-3-carbonyl)-amino-aryls (see German Patent No. 396,519 and British Patent No.

330,349); derivatives of l-hydroxy-naphthalene- 4-carboxylic acid (see U. S. Patent No. 1,453,660) as, for instance, 1 hydroxy-naphthalene4-phenyl-ketone; compounds containing an acidic methylene group capable of being combined with diazo-compounds as, for instance, pyrazolones and derivatives of beta ketone-aldehyde, for instance, aceto-acetyl amino-aryls' and di-(aceto-acetylamino) -aryls (see U. S. Patents No. 1,594,864,190.

1,594,866, No. 1,594,867, N0. 1,580,709, N0. 1,634,-

090) dihydroxy-quinolines (see U. S. Patents No. 1,820,039, No. 1,846,073, No. 1,846,074; British Patent No. 332,940) (2-hydroxy-carbazole-3- carbonyl) -amino-aryls, (2-hydroxy-benzocarbazole-3-carbonyl) -amino-ary1s, J (2-hydroxy-anthracene-3-carbonyl) -amino-aryls.

. These dyeing preparations yield when applied in an alkaline medium toifibers, by steaming only, insoluble azo-dyestufis on the fibers.

Such application to the fiber may consist in dyeing according to the one-bath method, or in printing; the dye-bath or the printing paste, or even the dyeing preparations themselves in powder form, are advantageously mixed with the usual dyeing or printing assistants having wetting, emulsifying or solvent properties, or also with the additional agents customarily used in nitrosamine-printingcolors, such as, for example, chromate.

The anti-diazo-sulfonic acids of the aforesaid constitution may be prepared in the usual man- No. 676,210. In Germany June 22, 1932 ner by transforming the amino group of the corresponding bases into the complex N=NSO3H. The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight:

(1) 252 parts of the sodium salt of 4-benzylamino 2.5 diamethoxybenzene 1 anti diazo sulfonic acid of 93% strength (obtainablefrom 1-amino-4-benzylamino 2.5 dimethoxybenzene, yellow powder), 150 parts of 2.3-hydroxynaph thoylv-amino-benzene and 98 parts of anhydrous 'sodium acetate are ground to form a homogeneous powder. There are obtained 500 parts of dyestufi preparation. A printing paste whichcontains 50 parts of the above dyestufi preparation, 20 parts of caustic soda solution of 34 Be, 20 parts of thiodiglycol, 20 parts of sodium chromate solution 1:4, 390 parts of water,

' 500 parts of starch tragacanth thickening is-printed on cotton material; the material is then dried and steamed for 5 minutes in. a Mather-Flatt apparatus. Thereupon, it is rinsed with an acid solution, soaped and rinsed.

A greenish blue print is obtained. By using the same anti-diazosulfonic acid together with 2.3-hydroxynaphthoyl-(1-amino-2- methoxybenzene) and 2.3-hydroxynaphthoyl- (l-aminor4-methoxy-2-metylbenzene), a dark blueprint, and by means of diacetoacetyl-4.4'- diamino 3.3 dimethyldiphenyl a red-orange print is obtained. i

(2) 143 parts of the potassium salt of 4-monon-butylamino 3-chlorobenzene-1-anti diazosulionic acid (obtainable from 1-amino-4-mono-nbutylamino-ii-chlorobenzene, light-yellow powder), 150 parts of 2.3-hydroerynaphthoyl-(1- ,amino-2-methyl-5-chlorobenzene) and 207 parts of anhydrous sodium acetate are ground to form a homogeneous powder. There are obtained 500 parts of dyestufi' preparation.

A printing paste, prepared from 50 parts of the above dyestufi preparation, 20 parts of caustic soda solution of 37 B., 20 parts of thiodiglycol, 20 parts of sodium chromate solution 1:4, 390 parts of water, 500 parts of starch 'tragacanth thickening,

is printed on the material; the material is dried, steamed for 10 minutes in a Mather-Flatt apparains and worked up as usual.

Acurrant print is thus obtained.

. chlorobenzene), 33 parts of ground sulfur and 147 parts of anhydrous sodium sulfite are ground to form a homogeneous powder. There are obtained 500 parts of dyestufi preparation.

A printing paste prepared from 50 parts of the above .dyestufi preparation, 20parts of caustic soda solution of 37 B., 20 parts of thiodi'glycol, 20 parts of sodium chromate solution 1:4, 390 parts of water, 500 parts of starch tragacanth thickening,

is printed upon the material and the latter is then worked up analogously to Example 1.

A navy blueprint is. obtained. (4) 320 parts of a press cake of 69.4% strength from the sodium salt of 2.5-dimethoxy-4-(26- dichlorobenzylamino) -benzene l-anti diazosulfonic acid, 150 parts of 2.3-hydroxynaphthoy1- (1-arninol-chlorobenzene) and 105 parts of anhydrous sodium acetate are ground until a dry powderis obtained; thereupon, 25 parts of ground caustic soda are added thereto and the whole is intimately mixed. There are obtained 600 parts of dyestuff preparation.

(5) 250 parts of the sodium salt of 4-methylamino-3chlorobenzene-l-anti-diazosulionic acid of 88.3% strength, 175 parts of the disodium salt of 2.3-hydroxynaphthoyl-(l-amino-Z-methylbenzene) and 75 parts of anhydrous sodium acetate are ground to form a homogeneous powder. Thereare obtained 500 parts of dyestuff preparation.

The process may be applied in the same manner to other kinds of fiber as, for instance, to viscose or to silk. I

By using other anti-diazosulfonic acids of the aforesaid kind and other azo components, the process may be performed in the same manner.

In the following table we have inserted the shades of a series of further dyeings or prints, produced in an analogous manner:

of this kind are the sulfonic acid, the carboxylic acid and the hydroxy group.

We claim: I

1. As new compositions of matter the dyeing preparations comprising an anti-diazo-sulfonate corresponding to the probable general formula ,preparations comprising an anti-diazo sulfonate corresponding to the probable general formula wherein R means an aralkyl radical and wherein the benzene nucleus may be substituted by halogen, aikyl or alkoxy, and a combining component containing a hydroXy or an O-alkali metal group whereof the adjacent position is capable of attaching an arylazo group, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuffs insoluble in water and alkalies.

3. As new compositions of matter the dyeing preparations comprising an anti-diazo-sulfonate corresponding to the probable general formula OOHa wherein R means a radical of the benzene series, and a combining component containing a hydroxy or an G-alkali metal group whereof the adjacent position is capable of attaching an arylazo group, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestufis insoluble in water and alkalies.

Antidiazosulfonic acid of: Azo-component Shade 1 l-amino-4-methylamino-3-chlorobenzene 2.3-hydroxynaphthoyl-(l-amino-2-methylbenzene) Reddish dark blue. 2 o. l-hydroxynaphthalene-4-phenylketone Brown. 3 Do 2.3-hydroxynaphthoyl-l-aminonaphthalene Reddish dark blue. 4 l-ammo--n utyla 2.3-hydroxynaphthoyl-1-amino-2.5-dimethoxy-benzene Deep garnet. 5 Do 2.3b-hydrox)ynaphthoyl(Lamina-2.5-dimethoxy-4-bromo- Bluish garnet. enzene 6 l )o 3-methyl-1-phenyl-5-pyrazolone Reddish yellow. 7 l-ammo-4-benzylam1n0-2-methylbenzene 2.3-hydroxynaphthoyl-(1amino4-methoxy-3-methylben- Reddish dark blue.

, zene 8 l-am irro-4-benzylamino-2-methylbenzene 2-hydrs)xy-anthracene-B-carbonybfl-amino-2 methylben- Green-blue.

zene 9 l-ami%o-4-(24'-dichlorobenzylamino) '2.5-dimeth- 2.3-hydroxynephth0yl-(1-amino-3-nitrobenzene) Blue.

oxy enzene. 10 Do 6 bromo 2.3 hydroxynaphthoyl (l amino 2.4 di- Dark blue.

methoxybenzene). 11 1-amnlio-4-(26-d1ch1orobenzylammo)-2.5-d1meth- 2.3-hydroxynaphthoyl-(l-aminonaphthalene) Greenish blue.

oxy enzene. 12 Do di -acetoacetyli.4i-diamino-3.3-dimethyldiphenyl Brownish orange.

Since an object of the present invention is to produce dyestuffs of good fastness properties which dyestufis are insoluble in Water and alkalies, it is to be understood that the aromatic nuclei of the general formula appearing in the appended claims contain nosubstituents as are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestufis to alkalies. Substituents 4. As new compositions of matter the dyeing preparations comprising an anti-diazo-sulfonate corresponding to the probable general formula OCHa H300 wherein R. means a radical of the benzene series,

7. A process which comprises applying to fibers the dyeing preparations claimed in claim 3, drying the fibers, thus applied to, steaming and finishing by rinsing and soaping.

8. A process which comprises applying to fibers the dyeing preparations claimed in clairri 4, drying the fibersthus applied to, steaming and finishing by rinsing and soaping.

ARTHUR ZITSCHER. WILI-IELM SEIDENFADEN. 

